Organometallics,
Год журнала:
2024,
Номер
43(16), С. 1662 - 1681
Опубликована: Апрель 17, 2024
C(sp3)–C(sp3)
bond
formation
is
gaining
more
prominence,
especially
with
a
growing
emphasis
on
building
three-dimensional
chemical
space
in
bioactive
molecules,
fine
chemicals,
and
agrichemicals.
Metallaphotoredox
catalysis
has
emerged
as
an
effective
strategy
for
designing
processes
using
diverse
C(sp3)
precursors
well
suited
1e–
radical
chemistry.
This
review
summarizes
the
latest
advancement
metallaphotoredox
catalysis,
addressing
long-standing
challenges
cross-coupling,
focus
classification
of
reactions
based
distinct
modes
activation
precursor
upon
entering
catalytic
cycle.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 20, 2024
Quaternary
carbon
centers
are
desirable
targets
for
drug
discovery
and
complex
molecule
synthesis,
yet
the
synthesis
of
these
motifs
within
traditional
cross-coupling
paradigms
remains
a
significant
challenge
due
to
competing
β-hydride
elimination
pathways.
In
contrast,
bimolecular
homolytic
substitution
(SH2)
mechanism
offers
unique
attractive
alternative
pathway.
Metal
porphyrin
complexes
have
emerged
as
privileged
catalysts
owing
their
ability
selectively
form
primary
metal–alkyl
complexes,
thereby
eliminating
challenges
associated
with
tertiary
alkyl
complexation
metal
center.
Herein,
we
report
an
iron-catalyzed
cross-electrophile
coupling
bromides
electrophiles
formation
all-carbon
quaternary
through
biomimetic
SH2
mechanism.
Vitamin
B12,
a
water-soluble
cobalt
complex,
is
inherently
predisposed
to
catalyze
reactions
under
aqueous
conditions.
Despite
its
potential,
adopting
this
strategy
for
transformations
of
hydrophobic
reagents
has
been
challenging,
because
their
low
solubility.
Here,
we
demonstrate
that
vitamin
B12
promotes
the
reaction
epoxides
and
aziridines
with
electrophilic
olefins
in
micellar
system.
The
desired
products
are
obtained
efficiently
fully
regioselective
manner.
This
green
catalytic
approach
further
advances
use
sustainable
catalysis
providing
valuable
method
synthesize
important
intermediates.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(46), С. 25293 - 25303
Опубликована: Ноя. 8, 2023
Catalytic
carboamination
of
alkenes
is
a
powerful
synthetic
tool
to
access
valuable
amine
scaffolds
from
abundant
and
readily
available
alkenes.
Although
number
approaches
have
been
developed
achieve
the
rapid
buildup
molecular
complexity
in
this
realm,
installation
diverse
carbon
nitrogen
functionalities
onto
unactivated
remains
underdeveloped.
Here
we
present
ligand
design
approach
enable
nickel-catalyzed
three-component
carboamidation
that
applicable
wide
range
alkenyl
derivatives
via
tandem
process
involving
alkyl
migratory
insertion
inner-sphere
metal-nitrenoid
transfer.
With
method,
various
can
be
installed
into
both
internal
terminal
alkenes,
leading
differentially
substituted
diamines
would
otherwise
difficult
access.
Mechanistic
investigations
reveal
tailored
Ni(cod)(BQiPr)
precatalyst
modulates
electronic
properties
presumed
π-alkene-nickel
intermediate
quinone
ligand,
enhanced
carbonickelation
efficiency
across
C═C
bond.
These
findings
establish
nickel's
ability
catalyze
multicomponent
with
high
exquisite
selectivity.
Organometallics,
Год журнала:
2024,
Номер
43(16), С. 1662 - 1681
Опубликована: Апрель 17, 2024
C(sp3)–C(sp3)
bond
formation
is
gaining
more
prominence,
especially
with
a
growing
emphasis
on
building
three-dimensional
chemical
space
in
bioactive
molecules,
fine
chemicals,
and
agrichemicals.
Metallaphotoredox
catalysis
has
emerged
as
an
effective
strategy
for
designing
processes
using
diverse
C(sp3)
precursors
well
suited
1e–
radical
chemistry.
This
review
summarizes
the
latest
advancement
metallaphotoredox
catalysis,
addressing
long-standing
challenges
cross-coupling,
focus
classification
of
reactions
based
distinct
modes
activation
precursor
upon
entering
catalytic
cycle.
